JP7011409B2 - Friction modifier and lubricating oil composition - Google Patents

Description

The present invention relates to a compound having a friction reducing effect, a friction modifier and a lubricating oil composition.

Continuously variable transmissions such as metal belt type, chain type, and toroidal type have been developed as transmissions used in automobiles. Since power is transmitted by a friction coefficient between a belt or a chain and a pulley in a continuously variable transmission, the lubricating oil for an automatic transmission used for these is required to have a friction coefficient between metals of a certain level or higher.

Lubricating oil needs to transmit power while protecting the friction surface by an oil film formed on the sliding portion. Therefore, the lubricating oil needs a certain friction coefficient, and improvement of the friction coefficient is strongly required especially in the field where energy saving is required. However, if the lubricating oil has a high coefficient of friction between metals, the noise resistance becomes low. That is, although there is a trade-off relationship between a high coefficient of friction between metals and noise resistance, there is a demand for a lubricating oil in which two values show good values at the same time, and a friction modifier constituting the lubricating oil.

The stepless transmission oil that is required to have both frictional force and noise resistance contains a lubricating oil base oil and a succinic acid imide compound, and is characterized by satisfying a specific inter-metal friction coefficient and a shader prevention life. The composition is disclosed (Patent Document 1: International Publication No. 2014/136911).

International Publication No. 2014/136911

However, the lubricating oil composition described in Patent Document 1 is not sufficient in terms of satisfying both the recent stricter coefficient of friction between metals and noise resistance. In particular, since the chain type continuously variable transmission is more likely to generate noise than the belt type continuously variable transmission, the lubricating oil composition is strongly required to have both a friction coefficient and noise resistance. There were no fully responsive friction modifiers and lubricant compositions.
The present invention has been made in view of the above circumstances, and there is a demand for a friction modifier and a lubricating oil composition having a high coefficient of friction between metals and high noise resistance.

As a result of diligent studies to solve the above problems, the present inventors synthesize a compound (Compound 1) represented by the formula (1) and use the compound in a friction modifier and a lubricating oil composition. This led to the completion of the present invention. That is, the present invention is as follows.

（式（１）中、Ｒ^１およびＲ^２はそれぞれ独立して下記式（２）で表される基またはＮＨＲ⁰であり（但し、Ｒ^１とＲ^２が同時に ＮＨＲ⁰ であることはない）、
Ｒ^０は水素または炭素数１以上２０以下のアルキル基、炭素数２以上３０以下のアルケニル基、炭素数６以上３０以下のアリール基、炭素数７以上３０以下のアルキルアリール基、炭素数７以上３０以下のアリールアルキル基のいずれか１であり、
Ｒ^３はそれぞれ独立して水素または炭素数１以上３０以下の炭化水素基であり、
ｌは０以上４以下の整数であり、
ｍは１以上４以下の整数であり（但し、Ｒ^１およびＲ^２が式（２）で表される基の場合、ｍは２以上４以下の整数である）、
ｎはそれぞれ独立して０以上４以下の整数である。）

（式（２）中、Ｒ^４は炭素数６以上２４以下の炭化水素基であり、
Ｘ^１およびＸ^２は、それぞれ独立して酸素原子または硫黄原子である。）
[２]
［１］に記載の化合物を含む摩擦調整剤。
[３]
基油および [２]に記載の摩擦調整剤を含む潤滑油組成物。
[４]
基油および［２］に記載の摩擦調整剤を含む無段変速機用潤滑油組成物。
[５]
[４]に記載の無段変速機用潤滑油組成物を用いる変速方法。 [1]
A compound represented by the following formula (1).

(In the formula (1), R ¹ and R ² are independently represented by the following formula (2) or NHR ⁰ (however, R ¹ and R ² are not NHR ⁰ at the same time). ,
^R0 is hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, and 7 or more carbon atoms. Any one of 30 or less arylalkyl groups,
R ³ is independently hydrogen or a hydrocarbon group having 1 or more and 30 or less carbon atoms.
l is an integer of 0 or more and 4 or less,
m is an integer of 1 or more and 4 or less (however, when R ¹ and R ² are groups represented by the formula (2), m is an integer of 2 or more and 4 or less).
n is an integer of 0 or more and 4 or less independently. )

(In the formula (2), ^R4 is a hydrocarbon group having 6 or more and 24 or less carbon atoms.
X ¹ and X ² are independently oxygen or sulfur atoms, respectively. )
[2]
A friction modifier containing the compound according to [1].
[3]
A lubricating oil composition containing a base oil and the friction modifier according to [2].
[4]
A lubricating oil composition for a continuously variable transmission, which comprises a base oil and the friction modifier according to [2].
[5]
A shifting method using the lubricating oil composition for a continuously variable transmission according to [4].

A preferred embodiment of the present invention provides a friction modifier having a high coefficient of friction between metals and high noise resistance.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the gist thereof.

1. 1. Compound 1
Compound 1 of the present invention is a compound represented by the above formula (1).
In the formula (1), R ¹ and R ² are independently represented by the following formula (2) or NHR ⁰ , but R ¹ and R ² are not NHR ⁰ at the same time. When R ¹ and R ² are NHR ⁰ at the same time, it is difficult to achieve both a high coefficient of friction between metals and high noise resistance.

R ³ is independently hydrogen or a hydrocarbon group having 1 or more and 30 or less carbon atoms. If R ³ is a hydrocarbon group having more than 30 carbon atoms, the noise resistance is inferior. R3 is preferably hydrogen ^, an alkyl group having 6 or more and 24 or less carbon atoms, an alkenyl group having 6 or more and 24 or less carbon atoms, an aryl group having 6 or more and 24 or less carbon atoms, and 7 or more and 24 or less carbon atoms, respectively, independently of each other. An alkylaryl group, an alkenylaryl group having 7 or more and 24 or less carbon atoms, an arylalkyl group having 7 or more and 24 or less carbon atoms, or an arylalkenyl group having 7 or more and 24 or less carbon atoms, more preferably independently of hydrogen. Alkyl groups with 10 or more and 22 carbon atoms, alkenyl groups with 10 or more and 22 carbon atoms, aryl groups with 10 or more and 22 carbon atoms, alkylaryl groups with 11 or more and 22 carbon atoms, and alkenyl aryls with 11 or more and 22 carbon atoms. A group, an arylalkyl group having 11 or more and 22 or less carbon atoms or an arylalkenyl group having 11 or more and 22 carbon atoms, and particularly preferably hydrogen, an alkyl group having 10 or more and 22 or less carbon atoms or 10 or more carbon atoms, respectively. 22 or less alkenyl groups.
^R0 is hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms or 7 or more carbon atoms. It is an arylalkyl group of 30 or less. If it is not the above functional group, its solubility in the base oil is inferior. ^R0 is preferably a hydrogen or an alkyl group having 1 or more and 15 or less carbon atoms, an alkenyl group having 2 or more and 15 or less carbon atoms or an aryl group having 6 or more and 15 or less carbon atoms, and more preferably hydrogen and 1 or more and 10 carbon atoms. The following alkyl group or alkenyl group having 2 or more and 10 or less carbon atoms.
Further, in the formula (2), ^R4 is a hydrocarbon group having 6 or more and 24 or less carbon atoms. A hydrocarbon group having less than 6 carbon atoms has poor solubility in the base oil, and a hydrocarbon group having more than 24 carbon atoms has poor noise resistance. Preferably, an alkyl group having 6 or more and 24 or less carbon atoms, an alkenyl group having 6 or more and 24 carbon atoms or less, an aryl group having 6 or more and 24 carbon atoms or less, an alkylaryl group having 7 or more and 24 carbon atoms or less, and 7 or more and 24 carbon atoms or less. An alkenylaryl group, an arylalkyl group having 7 or more and 24 or less carbon atoms, or an arylalkenyl group having 7 or more and 24 or less carbon atoms. ^R4 is more preferably an alkyl group having 10 or more and 22 or less carbon atoms or an alkenyl group having 10 or more and 22 or less carbon atoms, and particularly preferably an alkyl group having 14 or more and 20 or less carbon atoms or 14 or more and 20 or less carbon atoms. It is an alkenyl group.
In formula (2), X ¹ and X ² are independently oxygen atoms or sulfur atoms, respectively.

Examples of the alkyl group include various alkyl groups having a linear, branched chain or ring structure. Examples of the alkyl group having a ring structure include a cycloalkyl group, an alkylcycloalkyl group and a cycloalkylalkyl group. Examples of the cycloalkyl group include cycloalkyl groups having 5 or more and 7 or less carbon atoms such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group. The substitution position on the cycloalkyl ring is arbitrary.

Examples of the alkenyl group include various alkenyl groups having a linear, branched chain or ring structure. Examples of the alkenyl group having a ring structure include a cycloalkenyl group, an alkylcycloalkenyl group, an alkenylcycloalkyl group, a cycloalkenylalkyl group, a cycloalkenylalkenyl group and the like. The same applies to the cycloalkyl group. Examples of the cycloalkenyl group include cycloalkyl groups having 5 or more and 7 or less carbon atoms, such as a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group. Further, the substitution positions on the cycloalkenyl ring and the cycloalkyl ring are arbitrary.

Examples of the aryl group include phenyl (having a hydrocarbyl substituent), naphthyl and the like. Further, in the above-mentioned alkylaryl group, alkenylaryl group, arylalkyl group, and arylalkenyl group, the position of substitution with the aryl group is arbitrary.

Examples of the alkylaryl group include o-tolyl, m-tolyl, p-tolyl, 2,3-kissylyl, 2,4-kissylyl, 2,5-kissylyl, o-cumenyl, m-cumenyl, p-cumenyl, mesityl and the like. Can be mentioned.

Examples of the arylalkyl group include benzyl, phenethyl, diphenylmethyl, triphenylmethyl, 1-naphthylmethyl, 2-naphthylmethyl, 2,2-diphenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl and the like. Can be mentioned.

Further, in the formula (1), l is an integer of 0 or more and 4 or less, an integer of 0 or more and 3 or less is preferable, an integer of 1 or more and 3 or less is more preferable, and an integer of 2 or more and 3 or less is particularly preferable.
In the formula (1), m is an integer of 1 or more and 4 or less, but when R ¹ and R ² are groups represented by the formula (2), m is an integer of 2 or more and 4 or less. When m in the formula (1) exceeds 4, not only the solubility in the base oil is inferior, but also the coefficient of friction between metals is low and the noise resistance is inferior. Further, since the solubility in the base oil is increased, the coefficient of friction between metals is high, and the noise resistance is enhanced, m is preferably an integer of 2 or more and 3 or less, and R ¹ and R ² are represented by the formula (2). In the case of a coefficient, m is preferably an integer of 2 or more and 3 or less.
When m and n in the formula (1) are large, the solubility is lowered, so that n + m is preferably 1 or more and 6 or less, more preferably 1 or more and 5 or less, and particularly preferably 3 or more and 5 or less.

In the present specification, the "number of amino groups" is the sum of the value of m in the formula (1) and the number of NHR ^0s of the terminal groups (R ¹ , R ² ).
The number of amino groups in compound 1 represented by the formula (1) of the present invention is preferably 1 or more and 5 or less from the viewpoint of compatibility with base oil solubility, high coefficient of friction between metals and noise resistance. More than 4 or less is more preferable, and 2 or more and 4 or less is particularly preferable.

（上記式（Ａ）、（Ｃ１）および（Ｃ２）中、Ｒ^４、Ｘ^１およびＸ^２は、式（２）のＲ^４、Ｘ^１およびＸ^２と同様であり、上記式（Ｂ）、（Ｃ１）および（Ｃ２）中、Ｒ^３、ｌ、ｍおよびｎは式（１）のＲ^３、ｌ、ｍおよびｎと同様である） 2. 2. Synthesis of Compound 1 The method for producing Compound 1 of the present invention is not particularly limited, but can be synthesized, for example, as follows.
As shown in the following formulas (α) and (β), it can be obtained by an imidization reaction between a compound of the formula (A) such as 2-hydrocarbylsuccinic anhydride and a compound of the formula (B) such as diethylenetriamine.

(In the above formulas ( ^A ), (C1) and ( ^C2 ), ^R4 , X1 and X2 ^are the same as ^R4 , X1 and X2 of the above formula ( ² ), and the above formula (B), In (C1) and (C2), R3 ^, l, m and n are the same as R3 ^, l, m and n in the formula (1)).

Specifically, an organic solvent solution of the compound of the formula (A) (for example, a xylene solution) is added dropwise to an organic solvent solution of the compound of the formula (B) (for example, a xylene solution) while stirring, and the mixture is further stirred. Then, the compound 1 such as a succinimide compound can be synthesized by raising the temperature to about 150 ° C., stirring the mixture, and refluxing with xylene. At this time, it is preferable to gradually reduce the pressure using a diaphragm pump to completely reduce the pressure and distill off purified water and xylene.

Although 2-hydrocarbylsuccinic anhydride is available on the market, it may be synthesized by a known method described in Patent Document 1 (International Publication No. 2014/136911) in order to obtain an acid anhydride having a specific structure. ..

3. 3. Friction modifier The friction modifier of the present invention is a composition containing the compound 1 of the present invention.
The content of the compound 1 of the present invention in the friction modifier of the present invention is not particularly limited, but is preferable based on the total amount of the friction modifier from the viewpoint of achieving both a high coefficient of friction between metals and noise resistance. Is 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and may be 100% by mass.

4. Lubricating oil composition The lubricating oil composition of the present invention is a composition containing a base oil and the above-mentioned friction modifier of the present invention, and may further contain other components.
(Base oil)
The base oil contained in the lubricating oil composition of the present invention is not particularly limited, and any mineral oil or synthetic oil conventionally used as the base oil of the lubricating oil may be appropriately selected and used. can.
As the mineral oil, for example, the lubricating oil distillate obtained by distilling the atmospheric residual oil obtained by atmospheric distillation of crude oil under reduced pressure is subjected to solvent removal, solvent extraction, hydrocracking, solvent removal, and contact removal. Examples thereof include mineral oils that have been refined by performing one or more treatments such as waxing and hydrorefining. Examples thereof include mineral oil produced by isomerizing wax or GTL WAX (gas to liquid wax). Of these, mineral oil treated by hydrorefining is preferable.
Examples of the synthetic oil include poly-α-olefins such as polybutene, α-olefin homopolymers and copolymers (for example, ethylene-α-olefin copolymers), for example, polyol esters, dibasic acid esters, and phosphoric acid esters. Various esters such as, for example, various ethers such as polyphenyl ether, polyglycol, alkylbenzene, alkylnaphthalene and the like can be mentioned. Among these synthetic oils, poly-α-olefins and esters are particularly preferable, and those in which these two types are combined are also preferably used as synthetic oils.
In one embodiment of the present invention, the above-mentioned mineral oil may be used alone or in combination of two or more as the base oil. Further, the synthetic oil may be used alone or in combination of two or more. Further, one or more of the above mineral oils and one or more of the above synthetic oils may be used in combination.

The content of the base oil contained in the lubricating oil composition of the present invention is not particularly limited, but is preferably 60% by mass or more, more preferably 70% by mass or more and 98% by mass or less, and further preferably 70% by mass. It is 95% by mass or less.

(Friction modifier)
The friction modifier contained in the lubricating oil composition of the present invention is a composition containing the compound 1 of the present invention.
The content of the friction modifier contained in the lubricating oil composition of the present invention is not particularly limited, but the kinematic viscosity of the composition does not increase too much, and it is preferable from the viewpoint of solubility in the base oil and a high coefficient of friction between metals. It is 0.05% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 4% by mass or less, and further preferably 0.05% by mass or more and 2% by mass or less.
The amount of nitrogen (N amount) of the friction modifier is preferably 100 mass ppm or more and 3000 mass ppm or less, more preferably 150 mass ppm or more and 2500 mass ppm or less, and 200 mass ppm or more and 2000 mass ppm or less based on the total amount of the lubricating oil composition. It is particularly preferably ppm or less.

(Other ingredients)
The lubricating oil composition of the present invention may further contain other components as long as the effects of the present invention are not impaired. Other components include, for example, extreme pressure agents, lubricants, viscosity index improvers, pour point lowering agents, wear inhibitors, ashless dispersants, rust inhibitors, metal deactivators, defoamers, antioxidants. Examples thereof include additives usually used for lubricating oils such as.

Examples of extreme pressure agents include (mono, di, tri-thio) (sub) phosphoric acid esters, phosphorus compounds such as zinc dithiophosphate, and sulfurs such as disulfides, sulphide olefins, sulfide oils and fats, and dithiocarbamates. Examples include contained compounds. When these anti-wear agents are contained in the lubricating oil composition of the present invention, the content thereof is preferably 0.005% by mass or more and 5% by mass or less based on the total amount of the lubricating oil composition.

Examples of the cleaning agent include alkali metal sulfonate, alkaline earth metal sulfonate, alkali metal phenate, alkaline earth metal phenate, alkali metal salicylate, alkaline earth metal salicylate, and a mixture thereof. These detergents may be overbased. When the lubricating oil composition of the present invention contains a cleaning agent, the content thereof is not particularly limited. However, in the case of an automatic transmission or a continuously variable transmission, it is usually preferably 0.01% by mass or more and 5% by mass or less in terms of metal element equivalent amount based on the total amount of the lubricating oil composition.

Examples of the viscosity index improver include polymethacrylate (PMA) -based (for example, polyalkylmethacrylate, polyalkylacrylate, etc.), olefin-based copolymer (OCP) -based (for example, ethylene-propylene copolymer (EPC), and the like. Polybutylene, etc.), Styrene-based copolymers (for example, polyalkylstyrene, styrene-diene copolymers, styrene-isoprene copolymers, styrene-diene hydride copolymers, styrene-maleic anhydride copolymers, etc.) And so on. Examples of the PMA-based viscosity index improver include a dispersed type and a non-dispersed type. The dispersed PMA-based viscosity index improver is a homopolymer of alkyl methacrylate or alkyl acrylate, and the non-dispersive PMA-based viscosity index improver is a polar monomer having dispersibility with alkyl methacrylate or alkyl acrylate (for example). , Diethylaminoethyl methacrylate, etc.). Further, like the PMA-based viscosity index improver, the OCP-based viscosity index improver also includes a non-dispersion type and a dispersion type.

The mass average molecular weight (Mw) of these viscosity index improvers is usually 5,000 or more and 1,000,000 or less, and in the case of PMA-based viscosity index improvers, the mass average molecular weight (Mw) is preferably 20,000 or more. It is preferably 300,000 or less, more preferably 25,000 or more and 250,000 or less, and particularly preferably 25,000 or more and 200,000 or less. In the case of the OCP-based viscosity index improver, the mass average molecular weight (Mw) is preferably 5,000 or more and 800,000 or less, and more preferably 10,000 or more and 500,000 or less.
These viscosity index improvers may be used alone or in combination of two or more. From the viewpoint of improving the viscosity index, the blending amount is preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and particularly preferably 1.0% by mass or more, based on the total amount of the lubricating oil composition. Is. Then, it is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 9.5% by mass or less.

Examples of the flow point lowering agent include ethylene-vinyl acetate copolymer, condensate of chlorinated paraffin and naphthalene, condensate of chlorinated paraffin and phenol, and polymethacrylate (PMA) -based (polyalkylmethacrylate, polyalkyl). Acrylate and the like), polyalkylstyrene, polyvinylacetate, polybutene and the like, and PMA type is preferably used. The PMA-based pour point-lowering agent has the same chemical structure as the PMA-based viscosity index improver, but the pour point-lowering action is such that the side chain alkyl group ester-bonded to the main chain of PMA is the lubricating oil group. It is thought that the pour point is lowered by co-crystallizing with the wax content of the oil to adjust the direction of crystal growth and changing the crystal morphology of the wax. Examples of the mass average molecular weight of the PMA-based pour point lowering agent include those having a mass average molecular weight of 10,000 or more and 150,000 or less.
These pour point lowering agents may be used alone or in combination of two or more. The blending amount is preferably 0.01% by mass or more, more preferably 0.10% by mass or more, and preferably 10% by mass or less, more preferably 5 based on the total amount of the lubricating oil composition. It is 0.0% by mass or less, more preferably 1.0% by mass or less.

Examples of the anti-wear agent include a thiophosphate metal salt (example of the metal: zinc (Zn), lead (Pb), antimony (Sb)) and a thiocarbamic acid metal salt (example of the metal: zinc (Zn)). ), And phosphorus-based anti-wear agents such as phosphoric acid esters (eg, tricresyl phosphate). These anti-wear agents may be used alone or in combination of two or more. The blending amount of the wear inhibitor is preferably in the range of 0.05% by mass or more and 5.0% by mass or less based on the total amount of the lubricating oil composition.

Examples of the ashless dispersant include benzylamines, boron-containing benzylamines and the like. These ashless dispersants may be used alone or in combination of two or more.
The blending amount of the ashless dispersant is preferably in the range of 0.10% by mass or more and 20% by mass or less, more preferably 0.3% by mass or more and 10% by mass or less, based on the total amount of the lubricating oil composition.

Examples of the rust preventive agent include alkyl or alkenyl succinic acid derivatives such as dodecenyl succinic acid half ester, octadecenyl succinic acid anhydride, and dodecenyl succinic acid amide; fatty acid sicken; alkyl sulfonate; sorbitan monooleate, glycerin monoole. Polyhydric alcohol partial esters such as ate and pentaerythritol monooleate; amines such as rosinamine and N-oleylzalkosine; dialkylphosphiteamine salts; fatty acid amides; paraffin oxide; alkylpolyoxyethers and the like. These rust preventives may be used alone or in combination of two or more.
The blending amount of the rust preventive is preferably in the range of 0.01% by mass or more and 3.0% by mass or less based on the total amount of the lubricating oil composition.

Examples of the metal inactivating agent (examples of the metal; copper, iron) include benzotriazole, triazole derivative, benzotriazole derivative, thiadiazole derivative. These metal inactivating agents may be used alone or in combination of two or more.
The blending amount of the metal deactivating agent is preferably in the range of 0.01% by mass or more and 5.0% by mass or less based on the total amount of the lubricating oil composition.

Examples of the defoaming agent include silicone compounds such as dimethylpolysiloxane; and ester compounds such as polyacrylate. These defoaming agents may be used alone or in combination of two or more.
The blending amount of the defoaming agent is preferably in the range of 0.05% by mass or more and 5.0% by mass or less based on the total amount of the lubricating oil composition.

As the antioxidant, hindered phenol-based or amine-based ones, zinc alkyl dithiophosphate (ZnDTP) and the like are preferably used. As the hindered phenol type, a bisphenol type or an ester group-containing phenol type is preferable. As the amine type, dialkyldiphenylamine and naphthylamine type are preferable. These antioxidants may be used alone or in combination of two or more.
The blending amount of the antioxidant is preferably in the range of 0.05% by mass or more and 7.0% by mass or less based on the total amount of the lubricating oil composition.

5. Method for Producing Lubricating Oil Composition The method for producing the lubricating oil composition of the present invention is not particularly limited, but is obtained by mixing each component (base oil, friction modifier, and other components) contained in the lubricating oil composition. be able to.

6. Applications of Lubricating Oil Composition The compound represented by the formula (1) of the present invention, the friction modifier and the lubricating oil composition are suitably used for, for example, an automobile transmission and other transmissions, and in particular, continuously variable transmission. It is suitably used for a lubricating oil composition used for a transmission (for example, a metal belt type, a chain type continuously variable transmission, etc.).

Production Example 1 (Bisimide N = 3)
18.9 g (0.1 mmol) of tetraethylenepentamine and 30 ml of xylene were placed in a 200 ml separable flask equipped with a Dean-Stark cooling tube, a nitrogen blow tube, and a thermometer to prepare a xylene solution 1. On the other hand, 70.1 g (0.2 mmol) of isooctadecenyl succinic anhydride and 30 ml of xylene were mixed in an Erlenmeyer flask to make them uniform to prepare a xylene solution 2. The xylene solution 2 of isooctadecenyl succinic anhydride was added dropwise to the xylene solution 1 over 30 minutes with stirring. The temperature was raised to 100 ° C. and stirred for 1 hour, and further the temperature was raised to 150 ° C. and the mixture was stirred for 4 hours while refluxing xylene to obtain about 1.8 g of produced water. The nitrogen gas was stopped, the pressure was gradually reduced to 0.02 MPa with a diaphragm pump to distill off the approximate generated water and solvent xylene, and then the pressure was reduced to 2 mmHg with a vacuum pump to completely distill off the produced water and solvent xylene. .. The temperature was lowered to 80 ° C., nitrogen was added, and the pressure was returned to atmospheric pressure to obtain bisimide consisting of the target tetraethylenepentamine and isooctadecenyl succinic acid.

Production Example 2 (Monoimide N = 2)
The procedure was the same as in Production Example 1 except that 20.6 g (0.2 mmol) of diethylenetriamine was used instead of 18.9 g (0.1 mmol) of tetraethylenepentamine, and the target diethylenetriamine and isooctadecee were used. A monoimide consisting of nylsuccinic acid was obtained. The amount of water produced when the temperature was raised to 150 ° C. and refluxed with xylene was about 3.6 g.

Hereinafter, the present invention will be described in detail with reference to Examples, but the technical scope of the present invention is not limited thereto.

[Evaluation methods]
The evaluation methods in each Example and Comparative Example are as follows. (Friction coefficient between metals)
The coefficient of friction between metals was evaluated by attaching a jig equipped with three metal pins to the low-speed slip tester specified in JASO M349: 2010 and rubbing it against a metal plate. The test conditions for measuring the coefficient of friction between metals were as follows.
-Test equipment Metal pin Material: SUJ2
Metal plate material: SUJ2
·Test condition:
Oil temperature: 120 ° C
Rotation speed: 200 rpm
Load: 3600N

(Noise resistance)
The value (μ10 / μ200) obtained by dividing the friction coefficient at a rotation speed of 10 rpm by the friction coefficient at a rotation speed of 200 rpm was defined as the “μ ratio”. The friction coefficient at a rotation speed of 10 rpm was measured under the same conditions as the measurement of the friction coefficient between metals except for the rotation speed. For example, when the μ ratio is less than 1, the coefficient of friction between metals increases as the rotation speed increases, so that the noise decreases, whereas when the μ ratio exceeds 1, the coefficient of friction between metals decreases as the rotation speed increases. Therefore, the noise becomes large. Therefore, the lower the μ ratio, the better the noise resistance.

[Examples 1 and 2, Comparative Examples 1 and 3]
In Examples 1 and 2 and Comparative Examples 1 to 3 below, Comparative Example 1 is a reference example showing a standard of friction coefficient between metals and noise resistance. That is, the lubricating oil composition having a higher coefficient of friction between metals and a lower μ ratio than that of Comparative Example 1 (Reference Example) was used as an example, and the others were designated as Comparative Examples 2 and 3.

Each component was mixed based on the compounding composition shown in Table 1 to prepare a lubricating oil composition. The friction modifier used in Example 1 is the bisimide compound produced in Production Example 1, and the friction modifier used in Example 2 is the monoimide compound produced in Production Example 2.
Table 1 shows the results of the coefficient of friction between metals (μ200) and the μ ratio (μ10 / μ200) indicating noise resistance of these lubricating oil compositions.

As shown in Table 1, the lubricating oil composition of Example 1 using isooctadecenyl succinate bisimide (N = 3), which is a compound represented by the formula (1), as a friction modifier, and friction modifier. The lubricating oil composition of Example 2 using isooctadecenyl succinate monoimide (N = 2), which is a compound represented by the formula (1), contains the compound represented by the formula (1). Compared with the lubricating oil composition of Comparative Example 1, the coefficient of friction between metals (μ200) was high and the μ ratio (μ10 / μ200) was low.
The friction modifier used in the lubricating oil composition of Comparative Example 2 is polybutenyl succinate bisimide, and the compound is a succinate bisimide compound, but is not a compound represented by the formula (1). Comparative Example 2
The lubricating oil composition of No. 1 had a higher coefficient of friction between metals (μ200) than that of the lubricating oil composition of Comparative Example 1, but also had a higher μ ratio (μ10 / μ200).
The friction modifier used in the lubricating oil composition of Comparative Example 3 is isooctadecenyl succinate monoimide, not a compound represented by the formula (1). The lubricating oil composition of Comparative Example 3 had a lower coefficient of friction between metals (μ200) and a higher μ ratio (μ10 / μ200) than the lubricating oil composition of Comparative Example 1.

The lubricating oil composition using the compound 1 as a friction modifier can be used as a transmission oil, and can be used as an automatic transmission oil or a stepless transmission oil. In particular, it can be used as a belt-type or chain-type continuously variable transmission oil for automobiles and the like that require energy saving.

Claims (6)

Based on the total amount of lubricating oil composition, viscosity index improver is 0.5% by mass or more, detergent is 0.01-5% by mass, extreme pressure agent is 0.005-5% by mass, and friction modifier is 0.05. A lubricating oil composition containing -5% by mass and a base oil, wherein the friction modifier is a compound represented by the following formula (1).

(In the formula (1), R ¹ is a group represented by the following formula (2), and R ² is NHR ⁰ .
^R0 is hydrogen or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, and 7 or more carbon atoms. Any one of 30 or less arylalkyl groups,
R ³ is independently hydrogen or a hydrocarbon group having 1 or more and 30 or less carbon atoms (excluding a hydrocarbon group containing a substituent) .
l is an integer of 0 or more and 4 or less,
m is an integer of 1 or more and 3 or less ,
n is an integer of 0 or more and 4 or less independently. )

(In the formula (2), ^R4 is an alkenyl group having 14 or more and 20 or less carbon atoms.
X ¹ and X ² are independently oxygen or sulfur atoms, respectively. ) In the formula (1), R ³ is independently hydrogen or an alkyl group having 1 or more and 20 or less carbon atoms, an alkenyl group having 2 or more and 30 or less carbon atoms, an aryl group having 6 or more and 30 or less carbon atoms, and 7 or more carbon atoms. The lubricating oil composition according to claim 1, which is an alkylaryl group of 30 or less or an arylalkyl group having 7 or more and 30 or less carbon atoms. The lubricating oil composition according to claim 1 or 2, wherein the viscosity index improver has a mass average molecular weight (Mw) of 5,000 or more and 1,000,000 or less. The lubricating oil composition according to any one of claims 1 to 3, wherein the nitrogen amount (N amount) of the friction modifier is 100 mass ppm or more and 3000 mass ppm or less based on the total amount of the lubricating oil composition. A lubricating oil composition for a continuously variable transmission, which comprises the lubricating oil composition according to any one of claims 1 to 4. A shifting method using the lubricating oil composition for a continuously variable transmission according to claim 5.